加拿大玩具安全标准 Method C-03 2009版

Part B: Test Methods Section, Method C03Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),and Barium (Ba) in Applied Coatings. 701Scope1.1This method describes a general procedure for the determination of leachablearsenic, selenium, cadmium, antimony, and barium in decorative or protectivecoatings applicable to item 9(c) of Part I, Schedule I of the Hazardous ProductsAct ( SOR 2005-344 ).2Applicable Documents2.1Standard Practice for Use of the Terms Precision and Bias in ASTM TestMethods. Volume 14.02, ASTM E177-90a (1996), pp.79-90.2.2Standard Practice for Intra laboratory quality Control Procedures and aDiscussion on Reporting Low-Level Data. Volume 11.01, ASTM D4210-89,pp.412-419, 1998.2.3John Keenan Taylor, Quality Assurance of Chemical Measurements. LewisPublishers, INC. 328 pages, 1987.2.4National Standard of Canada - Methods of test for toxic trace elements inprotective coatings. CGSB Standard Test Method 1-GP-500.2, 1-GP-500.3, 1-GP-500.4, 1-GP-500.5, 1-GP-500.7. Specifications Board. (December, 1973).CGSB Standard Test Method 1-GP-500.2 (December, 1973).2.5 C. Watson, “Update of Method C-03, Determination of Leachable Cadmium (Cd),Barium (Ba), Antimony (Sb), Selenium (Se) and Arsenic (As) in AppliedCoatings.” Product Safety Laboratory, Project Report No. 2004-0801. (Nov.2004)2.6 A. Babcock, “Update of Method C-03, Determination of Leachable Arsenic (As),Selenium (Se), Cadmium (Cd), Antimony (Sb), and Barium (Ba) in AppliedCoatings.” Product Safety Laboratory, Project Report No. 2005-0881. (Oct.2007)Part B: Test Methods Section, Method C03Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),and Barium (Ba) in Applied Coatings. 703Reagents and Apparatus(Note 1)3.1ICP-MS Agilent 7500a equipped with an internal standards addition Tee3.2Arsenic, Selenium, Cadmium, Antimony and Barium standards, 1000 ppm, orAs, Se, Cd, Sb, Ba (+ others) multi-element standard 10.0 ppm ± 0.5%, SCPScience or equivalent, traceable to NIST, for calibration3.310.0 ppb As, Se, Cd, Sb, Ba calibration control standard3.4Gallium, Indium and Bismuth standards, 1000 ppm (nominal), SCP Science orequivalent, traceable to NIST, for internal standards3.5Ultra-pure (18.2 M S) water, free of As, Se, Cd, Sb, Ba3.6Hydrochloric acid, concentrated (- 37% w/w), Trace Metal Grade, FisherScientific3.7Nitric acid, concentrated (- 69% w/w), Trace Metal Grade, Fisher Scientific3.8Scalpel or other suitable scraping tool.3.9Tetrahydrofuran (THF) HPLC Grade, Caledon Laboratories, Ltd.3.10Electric grinder3.11Mortar and pestle3.12Air convection oven3.13Desiccator3.14Sieves, 250 and 500 :m mesh3.15Sample bottles for sieved paint3.16Analytical Balance, with a precision of 0.1mg3.17Weighing vessels3.18Glass beakers, 50 mL3.19Oscillating hot plate or magnetic stirrer3.20Filter paper, Whatman no. 403.21Funnels to fit 50 mL flasks or tubes3.22Volumetric flasks, 50 mL, 2 L3.23Sample tubes, screw cap, 50 mL certified volume3.24Pipettes adjustable 10 - 100 :L, 100 - 1000:L, 0.500 - 2.50 mL, 1.00 - 10.00 mL3.25NIST SRM 1633b, Coal Fly Ash, used as a controlNote 1:Equivalent materials and apparatus may be used.Part B: Test Methods Section, Method C03Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),and Barium (Ba) in Applied Coatings. 704Experimental Procedure4.1Scrape off the applied coating from the test sample with a scalpel, or othersuitable scraping tool, being careful not to remove any of the underlyingsubstrate material. Alternatively, the coating can be removed withtetrahydrofuran (THF) or a suitable solvent (Note 2), and collected into anappropriate vessel. Evaporate the solvent from the removed coating and dry toconstant weight (to the nearest 1 mg) in an air convection oven at 60°C ± 3°C.This may take several hours. Remove the vessel from the oven and cool in adesiccator.4.2Transfer the removed coating to a mortar and grind the sample with a pestle. Anelectric grinder may be used when the sample is too difficult to grind with a pestleand a mortar. Sieve the ground coating with a 500 :m sieve. The samplepassing through the 500 :m sieve is then sieved through a 250 :m sieve. Theportion of the ground coating that passes the 500 :m and does not pass the 250:m is used for the leaching test. Place the sieved portion in a weighing vesseland dry to constant weight (to the nearest 1 mg) in an air convection oven at60°C ± 3°C. This may take about an hour. Remove the vessel from the ovenand cool in a desiccator.4.3Prepare the 5% (v/v) HCl leaching solution by diluting 50 mL of concentrated(approx. 37% w/w) hydrochloric acid to 1000mL with ultra-pure water.4.4Transfer about 100 mg of the dried coating into a tared 100 mL beaker and weighto the nearest 0.1 mg. Add 20 mL of the 5% (v/v) HCl leaching solution andimmediately start stirring for 10 ± 1 minutes at 20°C ±3°C with the use of anoscillating hotplate or a magnetic stirrer. At the end of the 10 ± 1 minutes,immediately filter the solution, through a Whatman no. 40 filter paper in a funnel,into a 50 mL volumetric flask or certified 50 mL sample tube, wash with a few mLof ultra-pure water, add 1 mL of concentrated nitric acid, and make up to volumewith ultra-pure water. At least three replicate analyses should be performed oneach coating sample.4.5Prepare a blank solution by adding 20 mL of the 5% (v/v) HCl leaching solution toa 100 mL beaker and immediately start stirring for 10 ± 1 min. at 20ºC ± 3ºC withthe use of an oscillating hotplate or a magnetic stirrer. At the end of the 10 ± 1min. immediately filter the solution, through a Whatman no. 40 filter paperNote 2:Acetone or dichloromethane may be used to facilitate the removal of the applied coating, solvents like tetrahydrofuran should not be used if the test article's substrate material is a plastic.Part B: Test Methods Section, Method C03Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),and Barium (Ba) in Applied Coatings. 70 and a funnel, into a 50 mL volumetric flask or certified 50 mL sample tube, wash with a few mL of ultra-pure water, add 1 mL of concentrated nitric acid, and make up to volume with ultra-purewater.4.6Prepare a 2.0% (v/v) nitric acid diluting solution by diluting 20 mL of concentrated (approx. 69% w/w) nitric acid to 1000mL with ultra-pure water.4.7Dilute the worked-up leachate ten times using 2% (v/v) nitric acid (the 50 mLleachate from section 4.4).5Calibration5.1Prepare an acid solution consisting of 0.2% (v/v) hydrochloric acid and 2.0% (v/v)nitric acid in a 2 L volumetric flask. Use 4 mL of conc. HCl and 40 mL of conc.HNO 3 and make up to 2 L volume with ultra-pure water. This solution will beused as a blank solution, to prepare calibration standard solutions, and to dilute samples that are over the linear dynamic range of the instrument.5.2Prepare a series of at least three working calibration standards in the linearrange of the detector of the instrument to obtain a linear calibration curve with acorrelation coefficient of at least 0.99. These standards should be in the following range: 0 ppb to 100 or 200 ppb diluted from a 10 ppm solution of the five elements. Make up all calibration standards in 0.2% (v/v) hydrochloric acidand 2.0% (v/v) nitric acid.5.3Prepare about 100 - 250 mL of a 100 ppb solution of the internal standards Ga,In, Ba in 5% nitric acid. This solution is pumped into the internal standardaddition Tee (on the back of the peristaltic pump) where it mixes with the samplebefore going to the spray chamber of the ICP-MS.5.4Prepare separately from the standards a 10 ppb multi-element calibration controlsolution, or buy it ready-made with a NIST traceable certificate of analysis.5.5Analyse the calibration standards using a minimum of five replicate readings inthe ICP-MS method. Use the same ICP-MS method that will be used for theblanks, controls, and samples. Obtain a calibration curve of ion counts persecond vs. concentration and check it for suitability (e.g. outliers & linearity /curve fitting) for each element before proceeding with the analysis of thesamples.Part B: Test Methods Section, Method C03Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),and Barium (Ba) in Applied Coatings. 706Determination6.1Analyse the method blank before and after each batch of samples.6.2Check the calibration by analysing the 10 ppb multi-element calibration controlsolution. If the calibration is not in control, it may be necessary to re-make thecontrol solution and / or the calibration standards.6.3Analyse the control sample (NIST 1633b - coal fly ash) for all five elements.Record the results in the logbook method control chart (Use CCPro software).6.4Analyse the sample solutions using a minimum of five replicate readings in theICP-MS method. The use of nine or more replicate readings gives betterstatistics, but results in slightly longer analysis times. If necessary, dilute thesample with 0.2% HCl and 2.0% HNO 3 (as prepared in § 5.1) to keep the resultswithin the range of the calibration.7Calculations and Reporting7.1Calculate the percentage by weight of leachable elements in the dry coating testsample according to the following equation:Leachable elements % (w/w) = Ci × 50 × 10 × Dfm × 10,000,000where:Ci =Concentration of element in the leaching solution (ppb) from theinstrument § 6.450 =Volume of worked-up leachate (filtered, rinsed, acidified) § 4.510 =Dilution of leachate § 4.7Df =Further Dilution factor (if required to stay within calibration) § 6.4m =mass (g) of test sample used § 4.410,000,000 =ppb / percent7.2Where the quantity of sample for testing is sufficient and where practicable, theresult of analysis shall be reported as the average of a minimum of threeindependent replicate determinations having a precision which should not differmore than the specifications defined in section 8.Part B: Test Methods Section, Method C03Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb), and Barium (Ba) in Applied Coatings. 70Note 3:The standard deviation (s) of the test results may be calculated according to the following equation,where x i is the result of an individual determination, 0 is the average of the replicate determinations,and n is the total number of replicates.__________s = ' (x i ! 0)2 .r (n !1)7.3Where applicable, the average (x.x × 10 +e ) and the sample standard deviation (s.s × 10 e ) of replicate determinations (s for n > 2) shall be calculated (Note 3),and the result of analysis reported in the following format:Sample No.Specimen No.Colour /Description [As]Leachable % (w/w)[Se]Leachable % (w/w)[Cd]Leachable % (w/w)[Sb]Leachable % (w/w)[Ba]Leachable % (w/w)S-10012341A red paint (x.x±2s.s)×10+e (x.x±2s.s)×10+e (x.x±2s.s)×10+e (x.x±2s.s)×10+e (x.x±2s.s)×10+e S-10012342A blue paint (x.x±2s.s)×10+e (x.x±2s.s)×10+e (x.x±2s.s)×10+e (x.x±2s.s)×10+e (x.x±2s.s)×10+e8Quality Control Procedure8.1To ensure the proper operation of the instrument and that the precision of theanalytical measurements meet the specifications of the method, the followingquality control procedures shall be conducted concurrently with the analysis ofthe test sample.8.2The normal and correct operation of the ICP-MS shall be verified according to thefollowing guidelines:8.2.1Run the ICP-MS Tune program and verify that the values (ion counts persecond) for the tuning solution elements (typically Li Y Tl) are withinacceptable limits of the historical values. A slow decline in the numbers isto be expected as the detector wears out over a period of about twoyears. Record the tuning element values in the ICP-MS logbook andinclude a copy of the tune program printout in the sample or report file. Ifthe tuning values are too low, re-tune the instrument to get acceptablevalues. Minimum acceptable values are Li 6400, Y 16000, Tl 9600 .Part B: Test Methods Section, Method C03Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),and Barium (Ba) in Applied Coatings. 708.3The normal and correct operation of the test method shall be verified accordingto the following guidelines:8.3.1Conduct an analysis of the leachate of NIST SRM 1633b, coal fly ash,tested under identical experimental conditions (except for grinding andsieving) to those of the coating sample. Record the analytical test resultsfor all of the elements in the ICP-MS QC logbook. Verify that the resultsare within acceptable limits on the control chart, and if so, enter a note inthe sample folder(s) to the effect that the test method was found to be"within control". If the test results of the control sample fall outside thespecifications of the method, the entire analytical procedure shall berepeated.9Precision and Bias9.1Repeatability (r): The deviation between replicate test results, as obtained fromanalysis of NIST 1633b (coal fly ash) by the same analyst using the sameinstrument under constant operating conditions, in the normal and correctoperation of the test method, should not differ by more than the followingrepeatability limit at a 95% probability level (1.960 × %2 × CV% = 2.772 × CV%).As: 11%Se: 100%Cd: n/a Sb: n/a Ba: 50%9.2Bias: The bias cannot be established due to the absence of an accepted“leachable” reference value in paint.10Limit of Detection10.1The limit of detection (LOD) of this method, as determined by ICP-MS has beencalculated (Note 4) to be:Arsenic: 0.00018% (w/w)Selenium: 0.00015% (w/w)Cadmium: 0.00019% (w/w)Antimony: 0.00043% (w/w)Barium: 0.00041% (w/w)Note 4: ASTM test method D4210.Part B: Test Methods Section, Method C03Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),and Barium (Ba) in Applied Coatings. 7011Limit of Quantitation10.1The limit of quantitation (LOQ) of this method, as determined by ICP-MS hasbeen calculated (Note 5) to be :Arsenic: 0.00055% (w/w)Selenium: 0.00047% (w/w)Cadmium: 0.00059% (w/w)Antimony: 0.0013% (w/w)Barium: 0.0012% (w/w). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . End . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Note 5: ASTM test method D4210Part B: Test Methods Section, Method C03Determination of Leachable Arsenic (As), Selenium (Se), Cadmium (Cd), Antimony (Sb),and Barium (Ba) in Applied Coatings. 70 L:\QualityAssurance\Quality\BOOK5\ENGLISH\Amendment 70\C03 Effective 2009-06-15.wpd。